We have succeeded in achieving the heteroepitaxial growth of a delta-Bi2O3 thin film on a CaF2(1 1 1) substrate by means of chemical vapour deposition under atmospheric pressure. The film grew with a strong (I 1 1) orientation. From X-ray pole figures, it was observed that the delta-Bi2O3 film grew on the CaF2(1 1 1) substrate with 60 degrees rotational in-plane domains. The growth mode was of a 3D island type, and the grain size decreased with increasing oxygen pressure during the delta-Bi2O3 film growth, improving the overall surface smoothness. (c) 2006 Elsevier Ltd. All rights reserved.